ES2368721T5 - Herbicidal compositions containing N-phosphonomethylglycine and an auxin herbicide - Google Patents

Abstract

Herbicidal compositions are provided which cause rapid symptomology while delivering long term control of regrowth of plants. The herbicidal concentrate compositions comprise N-phosphonomethylglycine or a herbicidal derivative thereof, an auxin herbicide or a herbicidal derivative thereof, and at least one surfactant. Also provided is a method for killing or controlling the growth of certain plants by contacting the foliage of the plants with the diluted concentrate composition.

Description

DESCRIPTION

Herbicidal compositions containing N-phosphonomethylglycine and an auxin herbicide

Background

The present invention generally relates to herbicidal compositions or formulations and to methods of using such compositions to kill or control the growth and proliferation of unwanted plants. In particular, the present invention relates to herbicidal compositions, as well as their methods of use, comprising N-phosphonomethylglycine (glyphosate), or a herbicidal derivative thereof, and an auxin herbicide, or a herbicidal derivative thereof , optionally with one or more suitable surfactants. Such compositions cause early visual symptoms of treatment and / or enhanced effectiveness or control when applied to plant foliage.

Glyphosate is well known in the art as an effective post-emergent foliar application herbicide. In its acid form, glyphosate has a structure represented by the Formula:

and it is relatively insoluble in water (1.16% by weight at 25 ° C). For this reason, it is typically formulated as a water soluble salt.

Among the water-soluble salts of glyphosate is the potassium salt, which has a structure represented by the Formula:

in the ionic form predominantly present in aqueous solution at a pH of about 4. The potassium salt of glyphosate has a molecular weight of 207. This salt is disclosed, for example, by Franz in US Patent No. 4,405,531, as one of the "alkali metal" salts of glyphosate useful as herbicides, potassium being specifically disclosed as one of the alkali metals, along with lithium, sodium, cesium and rubidium. Example C discloses the preparation of the monopotassium salt by reacting specified amounts of glyphosate acid and potassium carbonate in an aqueous medium.

Herbicidal compositions comprising the herbicidal N-phosphonomethylglycine or derivatives thereof ("glyphosate") are useful for suppressing the growth of, or for killing, unwanted plants, such as grasses, weeds, and the like. Glyphosate is typically applied to the foliage of the target plant. After application, glyphosate is absorbed by the leaf tissue of the plant and travels throughout the plant. Glyphosate uncompetitively blocks an important biochemical pathway that is common to virtually all plants, but is absent in animals. Although glyphosate is very effective in killing or controlling the growth of unwanted plants, the uptake (i.e., absorption) of glyphosate by plant leaf tissue and the movement of glyphosate throughout the plant is relatively slow. Visual symptoms that a plant has been treated with glyphosate may not appear until a week or more after treatment.

WO02 / 096199 discloses herbicidal glyphosate compositions, including high glyphosate loading compositions, comprising glyphosate, a salt or an ester thereof, such as potassium glyphosate, and a surfactant and possibly stabilizer system. The examples disclose compositions comprising glyphosate and the auxin herbicide 2,4-D.

There is a continuing need for herbicidal compositions that show long-term control of unwanted plants and show early visual symptoms of treatment. These compositions would be appropriate for colder temperature applications, where early visual symptoms can be easily observed, while long-term control would improve as temperatures increased.

As is apparent from the disclosure that follows, these and other benefits are provided by the present invention.

Summary of the invention

The present invention provides aqueous herbicidal concentrate compositions comprising glyphosate or a herbicidal derivative thereof, an auxin herbicide and at least one first surfactant component, according to the claims.

Another embodiment of the present invention relates to a method for exterminating or controlling unwanted weeds or plants which comprises diluting an aqueous composition as claimed in an amount of water to form an application mixture and applying a herbicidally effective amount of the mixture of application to the foliage of unwanted weeds or plants.

Other objects and features of the present invention will be in part apparent and in part will be set forth hereinafter.

Detailed description

According to the present invention, herbicidal compositions containing glyphosate or a derivative thereof, an auxin herbicide or derivative thereof, and a suitable surfactant are provided, which are advantageous for a number of reasons, including early visual symptoms of plant treatment, uptake rapid control of the target plant and control of a broad spectrum of plant species, as well as more consistent, enhanced control of unwanted plants. Although the use of low application rates is not preferred, in at least some embodiments, lower application rates can be used without a significant loss of effectiveness of plant control.

Among the various aspects of the present invention is an aqueous herbicidal composition of N-phosphonomethylglycine (glyphosate), predominantly in the form of the potassium salt thereof, and an auxin herbicide. The word "predominantly", in the above context, means that at least about 50%, preferably at least about 55, 60, 65, 70, 75, 80, 85, 90, or about 95% by weight of glyphosate, Expressed as ea, it is present as the potassium salt. Other salts of glyphosate that may constitute the remainder of the glyphosate component are agriculturally acceptable salts, including the salts of isopropylamine, diammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine or trimethylsulfonium. The second ion salt should be chosen such that it does not adversely affect the viscosity, cloud point, non-crystallization, and other stability properties of the composition. The auxin herbicide is selected from the group consisting of 2,4-dichlorophenoxyacetic acid (2,4-D), 4- (2,4-dichlorophenoxy) butanoic acid (2,4-DB), dichloroprop, acid (4- chloro-2-methylphenoxy) acetic acid (MCPA), 4- (4-chloro-2-methylphenoxy) butanoic acid (MCPB), mecoprop, dicamba, picloram, quinclorac, agriculturally acceptable salts or esters of any of these herbicides and mixtures of the themselves. In one embodiment, preferably, the auxin herbicide is selected from the group consisting of 2,4-dichlorophenoxyacetic acid (2,4-D), dicamba, salts or esters thereof, and mixtures thereof. Generally, the main action of auxin herbicides appears to involve cell wall plasticity and nucleic acid metabolism. 2,4-D is thought to acidify the cell wall by stimulating the activity of a membrane-bound ATPase-driven proton pump. The reduction in apoplasmic pH induces cell elongation by increasing the activity of certain enzymes responsible for the loss of the cell wall. Low concentrations of 2,4-D are reported to stimulate RNA polymerase, resulting in subsequent increases in RNA, DNA, and protein biosynthesis. Abnormal increases in these procedures presumably lead to uncontrolled cell growth and division, resulting in destruction of vascular tissue. In contrast, high concentrations of 2,4-D and other auxin-type herbicides inhibit cell division and growth, usually in meristematic regions that accumulate photosynthate and herbicide assimilates from the phloem.

In another embodiment, preferably, the auxin herbicide is at least 1% soluble by weight in water at pH 6. The auxin herbicide may be present in the composition as its acid, an agriculturally acceptable salt (for example, of isopropylamine, diammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine, or trimethylsulfonium), or an agriculturally acceptable ester (for example, methyl, ethyl, propyl, butyl, octyl, ethoxyethyl, butoxyethyl or methoxypropyl). The salt or ester ion of the auxin herbicide should be chosen so as not to affect the viscosity, cloud point, non-crystallization and other stability properties of the composition. Glyphosate and auxin herbicidal compositions contain 65 g ae / l (grams of acid equivalent per liter) to 600 g glyphosate ae / l, preferably 75 to 600, 100 to 600, 150 to 600, of 200 to 600, 250 to 600, 300 to 600, 350 to 600, 400 to 600, 450 to 600, or 480 to 600 g glyphosate ae / l. In this context, generally, the weight ratio of glyphosate (acid equivalent base) to auxin herbicide (acid equivalent base) varies depending on the activity of the auxin herbicide which is generally determined using standard usage rates. One skilled in the art would know that a higher standard use rate indicates lower activity and thus more of the auxin herbicide should be used to achieve acceptable results. With this ratio in mind, in one embodiment, typically, the weight ratio of glyphosate to 2,4-D, 2,4-DB, MCPA, or MCPB is from about 10: 1 to 100: 1. In another embodiment, Typically, the weight ratio of glyphosate to mecoprop is 10: 1 to 50: 1. In yet another embodiment, typically, the weight ratio of glyphosate to dicamba or picloram is from 20: 1 to 200: 1. In a further embodiment, preferably, the weight ratio of glyphosate to 2,4-D is from 20: 1 to 100: 1; more preferably 20: 1 to 50: 1; particularly from 25: 1 to 50: 1. In a still further embodiment, preferably, the weight ratio of glyphosate to dicamba is from 40: 1 to 200: 1; more preferably 40: 1 to 100: 1; in particular, from 50: 1 to 100: 1.

In another embodiment of the invention, the glyphosate in the herbicidal glyphosate and auxin compositions is present in an amount of at least about 75, 100, 125, 150, 175, 200, 225; 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 480, 500, 525, 550, 575, 580 or 600 g a.s./l.

In another embodiment, the herbicidal component glyphosate (ea base) and auxins (ea base) are present in compositions of the invention in a weight ratio of at least 33: 1, 34: 1, 35: 1, 36 : 1, 37: 1, 38: 1, 39: 1, 40: 1, 45: 1, 50: 1, 55: 1, 60: 1, 65: 1, 70: 1, 75: 1, 80: 1 , 85: 1, 90: 1, 95: 1, 100: 1, 110: 1, 120: 1, 130: 1, 140: 1, 150: 1, 160: 1, 170: 1, 180: 1, 190 : 1 or 200: 1. In another embodiment, the herbicidal component glyphosate (ea base) and auxins (ea base) are present in a weight ratio of 40: 1 to 200: 1, 50: 1 to 200: 1, 60: 1 to 200: 1, 50: 1 to 150: 1, 50: 1 to 100: 1, or 32: 1 to 50: 1.

In another embodiment, the herbicidal component glyphosate (ea base) and auxins (ea base) are present in compositions of the invention in a weight ratio of at least 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 15: 1, 20: 1, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, 50: 1, 55: 1, 60: 1, 65: 1, 70: 1, 75: 1, 80: 1, 85: 1, 90: 1, 95: 1, 100: 1, 110: 1, 120: 1, 130: 1, 140: 1, 150: 1, 160: 1, 170: 1, 180: 1, 190: 1 or 200: 1.

Glyphosate is present in an amount of at least 65 g of e.a./l. In one embodiment, the glyphosate concentration is between 360 and 445 g ae / l and the herbicidal component glyphosate (ea base) and auxins (ea base) are present in a weight ratio of 5: 1 to 50: 1, 5: 1 to 40: 1 or 8: 1 to 36: 1. In a second embodiment, the glyphosate concentration is between 445 and 480 g ae / l and the herbicidal component glyphosate (ea base) and auxins (ea base) are present in a weight ratio of about 41: 1, 42: 1, 43: 1, 44: 1, 45: 1, 46: 1, 47: 1, 48: 1, 49: 1, 50: 1, 51: 1, 52: 1, 53: 1, 54: 1, 55: 1, 56: 1, 57: 1, 58: 1, 59: 1, 60: 1, 61: 1, 62: 1, 63: 1, 64: 1, or 65: 1. In a third embodiment, the glyphosate concentration is between 360 and 525 g ae / l and the herbicidal component glyphosate (ea base) and auxins (ea base) are present in a weight ratio of about 8: 1 to about 80: 1 or from about 25: 1 to about 56: 1. In a fourth embodiment, the glyphosate concentration is at least 480 g ae / l and the herbicidal component glyphosate (ae base) and auxins (ae base) are present in a weight ratio of about 25: 1 to about 80: 1, about 50: 1 to about 80: 1, about 63: 1 to about 80: 1, or about 25: 1 to about 52: 1.

The selection of application rates that are herbicidally effective for a composition of the invention is within the skill of the normal agricultural scientist. Those of skill in the art will also recognize that individual plant conditions, climatic conditions and growth, as well as the specific active ingredients and their weight ratio in the composition, will influence the degree of herbicidal effectiveness achieved by putting into the practice of the present invention. Typical application rates of the glyphosate and auxin herbicidal compositions of the present invention can be determined from the label of each commercially available herbicide for a particular weed species. In general, the glyphosate application rate is approximately 0.084 grams per square meter. A person skilled in the art will understand that when weed growth is tight or dense or in cases where weeds are growing in an undisturbed area, a higher application rate may be necessary to achieve control of acceptable weeds. Also, in difficult-to-control weeds, a higher application rate may be necessary for proper weed control.

The herbicidal potassium glyphosate and auxin composition of the present invention is useful in the control of a variety of leafy weeds. These weeds include abutilon, red yuyo, yuyo species, common hemp, giant ragweed, chestnut mustard, stink, quenopodia, common wild poinsettia, common mallow, sesbania, AIDS, wild mustard, ipomea (from Brazil), ipomea, marigold, faced bluebells, buckwheat, coup grass, primrose, common chickweed, chicken grass and spider plant.

Also provided by the present invention is a method of killing or controlling unwanted weeds or vegetation which comprises diluting with a suitable volume of water a herbicidally effective amount of a composition as provided herein to form an application mixture and apply the Application mixture to weed foliage or unwanted vegetation. If desired, the user can mix one or more adjuvants with a composition of the invention and the dilution water when preparing the application composition. Such adjuvants can include additional surfactant and / or an additional inorganic salt, such as ammonium sulfate, with the aid of further enhancement of herbicidal efficacy. However, under most conditions, a herbicidal method of use of the present invention gives acceptable efficacy in the absence of such adjuvants.

In a particular method contemplated for the use of a composition of the invention, the composition, after dilution in water, is applied to the foliage of crop plants genetically transformed or selected to tolerate glyphosate and, simultaneously, to the foliage of weeds or unwanted plants growing in close proximity to such crop plants. This method of use results in the control of unwanted weeds or plants, while leaving the crop plants substantially unscathed. Genetically transformed or selected to tolerate glyphosate crop plants include those whose seeds are sold by Monsanto Company or with permission from Monsanto Company that carry the Roundup Ready® trademark. These include varieties of wheat, grass, and corn.

Plant treatment compositions can be prepared simply by diluting a concentrated composition of the invention in water. The application of plant treatment compositions to the foliage is preferably carried out by spraying, using any conventional means for spraying liquids, such as spray nozzles, atomisers or the like. The compositions of the invention can be used in precision agriculture techniques, in which apparatus are used to vary the amount of pesticide applied to different parts of a field, depending on variables, such as the particular plant species present, the composition of the soil , etc. In one embodiment of such techniques, a global positioning system operated with the spray apparatus can be used to apply the desired amount of the composition to different parts of a field.

A plant treatment composition is preferably diluted enough to be easily sprayed using standard agricultural spray equipment. Useful spray volumes for the present invention can range from about 10 to about 1,000 liters per hectare (l / ha) or more per spray application.

High load

In a further embodiment, the herbicidal glyphosate and auxin compositions may contain from about 300 to about 600 g a.s./l of glyphosate, predominantly in the form of the potassium salt thereof. In these compositions, the remainder of the glyphosate component is made up of agriculturally acceptable salts including the salts of isopropylamine, monoethanolamine, n-propylamine, methylamine, ethylamine, ammonium, diammonium, hexamethylenediamine, dimethylamine or trimethylsulfonium. In another embodiment, preferably, the herbicidal glyphosate and auxin compositions may contain from about 450 to about 600 g a.s./l of glyphosate, predominantly in the form of the potassium salt thereof. In general, as the glyphosate concentration in the composition increases, the auxin herbicide concentration can be decreased to achieve acceptable weed control. Typically, in potassium glyphosate and auxin herbicidal compositions containing from about 450 to about 600 g ae / L of glyphosate, the weight ratio of glyphosate to auxin herbicide is from about 25: 1 to about 100: 1 . In particular, in potassium 2,4-D glyphosate compositions containing from about 540 to about 600 g ae / L of glyphosate, the weight ratio of glyphosate to 2,4-D is about 25: 1 to approximately 50: 1.

Surfactants

Effective surfactants and cosurfactants in glyphosate formulation, such as glyphosate potassium or glyphosate isopropylamine, with auxin herbicides include cationic, nonionic, anionic and amphoteric surfactants, as claimed, in which the surfactant component is present in an amount of at least 5% by weight based on the total weight of the composition.

Effective cationic surfactants in such glyphosate formulations include:

(i) dialkoxylated quaternary ammonium salt having the Formula:

(R120) ^x R13 X '

R11 ----- N I + ------ (R120) and R13 (2)

R14

wherein R11 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R12 in each of the groups x (R12O) and y (R12O) is independently ethylene or propylene, R13 is hydrogen or methyl, R14 is a straight or branched alkyl group having 1 to about 6 carbon atoms, the sum of x and y is an average number of about 2 to about 15, and X 'is an agriculturally acceptable anion;

(ii) monoalkoxylated quaternary ammonium salts having the Formula:

R25 X '

R21 ----- N + ----- (R220) x2R23 (3)

R24

wherein R21 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R24 and R25 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms, R22 in each of the groups x2 (R22O) is independently ethylene or propylene, R23 is hydrogen or methyl, x is an average number from about 5 to about 25, and X- is an agriculturally acceptable anion; Y

(iii) quaternary ammonium salts having the Formula:

wherein R31 is a linear or branched alkyl group having from about 8 to about 16 carbon atoms and R32, R33 and R34 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms and X- is an agriculturally acceptable anion.

In the aqueous concentrated formulations of the present invention, the proportion (by weight) of the e.a. of glyphosate to surfactant is typically in the range of from about 1: 1 to about 20: 1, preferably from about 2: 1 to about 10: 1, more preferably from about 2: 1 to about 8: 1, even more preferably from 2: 1 to about 6: 1, even more preferably about 3: 1 to about 6: 1, and even more preferably about 4.5: 1 to 6: 1.

In one embodiment of the invention, the density of the formulation of the invention is preferably at least 1,210 grams / liter, more preferably at least about 1,215, 1,220, 1,225, 1,230, 1,235, 1,240, 1,245, 1,250, 1,255, 1,260, 1,265 , 1,270, 1,275, 1,280, 1,285, 1,290, 1,295, 1,300, 1,305, 1,310, 1,315, 1,320, 1,325,1,330, 1,335, 1,340, 1,345, 1,350, 1,355, 1,360, 1,365, 1,370, 1,375, 1,380, 1,385, 1,390 , 1,395, 1,400, 1,405, 1,410, 1,415, 1,420, 1,425, 1,430, 1,435, 1,440, 1,445, or 1,450 g / liter.

As further discussed herein, other additives, adjuvants, or ingredients of the present invention may be introduced into the formulations to enhance certain properties of the resulting formulations. Although the formulations of the present invention generally show good overall viscosity and stability properties without the addition of any additional additives, the addition of a solubilizer (also commonly referred to as a cloud point enhancer or stabilizer) can significantly improve the properties of the formulations of the present invention. Suitable solubilizers for use with the novel formulations of the present invention include, for example, cocoamine (Armeen C), dimethylcocoamine (Arquad DMCD), cocoammonium chloride (Arquad C), PEG 2 cocoamine (Ethomeen C12), PEG 5 tallow (Ethomeen T15) and PEG 5 cocoamine (Ethomeen C15), all of which are made by Akzo Nobel (California). Additional excipient ingredients may include conventional formulation additives, such as dyes, thickeners, crystallization inhibitors, antifreeze agents (for example, glycols, such as ethylene glycol, or polyethylene glycols, such as polyethylene glycol 200, 400, 600, 1500, 4000 or 6000), foam moderating agents (for example, Antifoam ™ or Y-14088 Antifoam ™, both available from Crompton Corporation), anti-drift agents, compatibilizing agents, antioxidants (for example, ascorbic acid and sodium sulfite, in order , for example, to avoid the formation of a nitrosamine), other cosolvents (for example, N-methylpyrrolidone, d Ms O, DMF, propylene or ethylene glycol carbonate), or some other agent added to reduce or overcome the antagonism associated with the hard water (eg ammonium sulfate, EDTA, or a polymeric water conditioner, such as a polyacrylic acid).

Other components, such as solvents and organic acids, can be added to enhance the stability of the concentrate. These additives generally function to increase the solubility or dispersibility of the surfactants in the aqueous vehicle, thus allowing the formulation of resistant concentrates that exhibit enhanced pH and thermal stability, reduced viscosity, and high glyphosate loading. Non-limiting examples of water soluble solvents include acetates, C1-6 alkanols, C1-6 diols, C1-6 alkyl ethers or alkylene glycols and polyalkylene glycols and mixtures thereof. The alkanol can be selected from methanol, ethanol, n-propanol, isopropanol, the various positional isomers of butanol, pentanol, and hexanol, and mixtures thereof. It may also be possible to use in addition to, or instead of, said alkanols, diols, such as methylene glycols, ethylene glycols, diethylene glycols, propylene glycols, dipropylene glycols and butylene glycols and mixtures thereof and including polyalkylene glycols. These components are generally used in dispersion-effective or solubilization-effective amounts.

Suitable organic acids include, but are not limited to, acetic, dichloroacetic, citric, malic, oxalic, salicylic, and tartaric. Effective organic acid concentrations are generally between about 0.1% by weight and 5% by weight.

Although additional herbicides other than glyphosate and auxin herbicides may be included in compositions of the invention, it is preferred that glyphosate and auxin herbicides are the only herbicides in the composition.

Definitions

The terms "hydrocarbon" and "hydrocarbyl", as used herein, describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl, and alkynyl. Unless otherwise indicated, these moieties preferably comprise 1 to 30 carbon atoms.

The term "hydrocarbylene", as used herein, describes radicals attached at the two ends thereof to other radicals in an organic compound and consisting exclusively of the elements carbon and hydrogen. These moieties include alkylene, alkenylene, alkynylene, and arylene moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl, and alkynyl. Unless otherwise indicated, these moieties preferably comprise 1 to 30 carbon atoms.

The "substituted hydrocarbyl" moieties described herein are hydrocarbyl moieties that are substituted with at least one atom other than carbon, including moieties in which a carbon chain atom is substituted with a heteroatom, such as nitrogen, oxygen, silicon. , phosphorus, boron, sulfur or a halogen atom. These substituents include halogen, heterocycle, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide, ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine, amidine, phosphate, amine oxide and quaternary ammonium salt.

The "substituted hydrocarbylene" moieties described herein are hydrocarbylene moieties that are substituted with at least one atom other than carbon, including moieties in which a carbon atom is substituted with a heteroatom, such as nitrogen, oxygen, silicon, phosphorus. , boron, sulfur or a halogen atom. These substituents include halogen, heterocycle, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide, ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine, amidine, phosphate, amine oxide and quaternary ammonium salt.

Unless otherwise indicated, the alkyl groups described herein are preferably lower alkyls containing from one to 18 carbon atoms in the main chain and up to 30 carbon atoms. They can be straight or branched chain or cyclic and include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hexyl, 2-ethylhexyl, and the like.

Unless otherwise indicated, the alkenyl groups described herein are preferably lower alkenyls containing from two to 18 main chain atoms and up to 30 carbon atoms. They can be straight or branched chain or cyclic and include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and the like.

Unless otherwise indicated, the alkynyl groups described herein are preferably lower alkynyl containing from two to 18 carbon atoms in the main chain and up to 30 carbon atoms. They can be straight or branched chain and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like.

The terms "aryl", as used herein, alone or as part of another group designate optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing 6 to 12 carbon atoms in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl are the most preferred aryl.

The term "aralkyl", as used herein, designates a group that contains both alkyl structures and aryl structures, such as benzyl.

As used herein, alkyl, alkenyl, alkynyl, aryl, and aralkyl groups may be substituted with at least one non-carbon atom, including moieties in which a carbon chain atom is substituted with a heteroatom, such as nitrogen, oxygen, silicon, phosphorus, boron, sulfur, or a halogen atom. These substituents include hydroxy, nitro, amino, amido, nitro, cyano, sulfoxide, thiol, thioester, thioether, ester and ether, or any other substituent that can increase the compatibility of the surfactant and / or its enhancement of efficacy in the formulation of potassium glyphosate without adversely affecting the storage stability of the formulation.

The terms "halogen" or "halo", as used herein, alone or as part of another group refer to chlorine, bromine, fluorine and iodine. Fluorine substituents are often preferred in surface active compounds.

Unless otherwise indicated, the term "hydroxyalkyl" includes alkyl groups substituted with at least one hydroxy group and includes bis (hydroxyalkyl) alkyl, tris (hydroxyalkyl) alkyl, and poly (hydroxyalkyl) alkyl groups. Preferred hydroxyalkyl groups include hydroxymethyl (-CH2OH) and hydroxyethyl (-C2H4OH), bis (hydroxymethyl) methyl (-CH (CH2OH) 2), and tris (hydroxymethyl) methyl (-C (CH2OH) 3).

The term "cyclic", as used herein, alone or as part of another group designates a group that has at least one closed ring and includes alicyclic, aromatic (arene), and heterocyclic groups.

The terms "heterocycle" or "heterocyclic", as used herein, alone or as part of another group designate optionally substituted, fully saturated or unsaturated, monocyclic or bicyclic, aromatic or non-aromatic groups having at least one heteroatom in at least one ring and preferably 5 or 6 atoms in each ring. The heterocycle group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and / or 1 to 4 nitrogen atoms in the ring and can be attached to the rest of the molecule through a carbon or heteroatom. Exemplary heterocycle includes heteroaromatic compounds, such as furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl and the like, and non-aromatic heterocyclics, such as tetrahydrofuryl, tetrahydrothienyl, piperidinyl, pyrrolidino, etc. Exemplary substituents include one or more of the following groups: hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, cyano, thiol, thioester, thioether, ketal, acetal, ester and ether.

The term "heteroaromatic", as used herein, alone or as part of another group designates optionally substituted aromatic groups having at least one heteroatom in at least one ring and preferably 5 or 6 atoms in each ring. The heteroaromatic group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and / or 1 to 4 nitrogen atoms in the ring and can be attached to the rest of the molecule through a carbon or heteroatom. Exemplary heteroaromatic compounds include furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl and the like. Exemplary substituents include one or more of the following groups: hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, cyano, thiol, thioether, thioester, ketal, acetal, ester and ether. The term "acyl", as used herein, alone or as part of another group designates the moiety formed by removal of the hydroxyl group from the -COOH group of an organic carboxylic acid, eg, RC (O) -, in where R is R1, R1O-, R1R2N- or R1S-, R1 is hydrocarbyl, heterosubstituted hydrocarbyl or heterocycle and R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl.

The term "acyloxy", as used herein, alone or as part of another group designates an acyl group, as described above, attached through an oxygen bond (--O--), for example , RC (O) O-, where R is as defined in relation to the term "acyl".

The term "pesticide" includes chemicals and microbial agents used as active ingredients in products for the control of crop and grass pests and diseases, animal ectoparasites and other pests in public health. The term also includes plant growth regulators, pest repellants, synergists, herbicide protectants (which reduce the phytotoxicity of herbicides to crop plants) and preservatives, the administration of which to the target can expose the dermal tissue and especially the eye to the pesticide. Such exposure may arise from drift of the pesticide from the means of administration to the person carrying out the application of the pesticide or who is present in the vicinity of an application.

When a maximum or minimum "average number" is listed herein with reference to a structural characteristic, such as oxyethylene units or glucoside units, it will be understood by those skilled in the art that the integer number of such units in individual molecules in a surfactant preparation it typically ranges over a range that may include integers greater than the maximum or less than the minimum "average number". The presence in a composition of the individual surfactant molecules having an integer number of such units outside the range stated in "average number" does not eliminate the composition from the scope of the present invention, provided that the "average number" is within the established range. and other requirements are met.

By "storage stable", in the context of a concentrated aqueous glyphosate salt composition that additionally contains a surfactant and an auxin herbicide, it is meant that it does not exhibit phase separation on exposure to temperatures up to about 50 ° C and preferably that it does not form crystals of glyphosate or salt thereof on exposure to a temperature of about 0 ° C for a period of up to about 7 days (ie, the composition should have a crystallization point of 0 ° C or less). In aqueous solution concentrates, high temperature storage stability is often indicated by a cloud point of about 50 ° C or more. The cloud point of a composition is It is normally determined by heating the composition until the solution becomes cloudy and then allowing the composition to cool, with stirring, while its temperature is continuously controlled. A temperature reading taken as the solution clears is a measure of the cloud point. A cloud point of 50 ° C or more is normally considered acceptable for most commercial purposes for a glyphosate SL formulation. Ideally, the cloud point should be 60 ° C or more and the composition should withstand temperatures as low as about -10 ° C, preferably as low as about -20 ° C, more preferably as low as about -30 ° C, during up to about 7 days without phase separation (ie, without separation of frozen water or solid insoluble surfactant from the composition) and without crystal growth (even in the presence of initiator crystals of the glyphosate salt).

Herbicidal effectiveness is one of the biological effects that can be enhanced by the present invention. "Herbicidal effectiveness", as used herein, refers to any observable measure of plant growth control, which may include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation and (3) eliminate, destroy or otherwise diminish the appearance and activity of plants. The herbicidal effectiveness data set forth herein reports "control" as a percentage following a standard procedure in the art that reflects a visual assessment of plant mortality and growth reduction compared to untreated plants, performed by technicians specially trained to make and record such observations. In all cases, a single technician performs all percent control evaluations within any one experiment or trial. Such measurements are dependent on and regularly reported by the Monsanto Company in the course of its herbicide business.

Examples

The spray compositions of the following Examples contain an exogenous chemical, such as glyphosate salt as indicated, in addition to the listed excipient ingredients. The amount of exogenous chemical was selected by providing the desired rate in grams per hectare (g / ha) when applied in a spray volume of 93 I / ha. Various rates of exogenous chemical were applied for each composition. Thus, except where otherwise noted, when the spray compositions were tested, the exogenous chemical concentration varied in direct proportion to the exogenous chemical rate, but the excipient ingredient concentration remained constant across different exogenous chemical rates.

In the following illustrative Examples of the invention, greenhouse and field tests were conducted evaluating the relative herbicidal effectiveness of glyphosate compositions. Standard compositions included for comparison purposes include the following:

STD1: 725 g / l of glyphosate potassium salt in aqueous solution with no added surfactant.

STD2: 50% by weight of IPA salt of glyphosate in aqueous solution together with a surfactant. This formulation is sold by Monsanto Company under the trademark ROUNDUP ULTRAMAX®.

STD3: 570 g / I of glyphosate IPA salt in an aqueous solution with no added surfactant.

Different excipients were used in the compositions of the Examples. They can be identified as follows.

Cationic Surfactants:

(continuation)

Non-ionic surfactants:

Other components:

(continuation)

The following greenhouse test procedure was used to evaluate compositions of the Examples for herbicidal effectiveness, except where otherwise noted.

The seeds of the indicated plant species were planted in 88-mm square pots in a soil mixture that was previously sterilized and pre-fertilized with a slow-release 14-14-14 NPK fertilizer at a rate of 3.6 kg / m3. pots were placed in a greenhouse with sub-irrigation. Approximately one week after emergence, sprouts were diminished as needed, including removal of any unwanted or abnormal plants, to create a uniform series of test pots.

The plants were kept for the duration of the test in the greenhouse where they received a minimum of 14 hours of light per day. If natural light was insufficient to meet the daily requirement, artificial light with an intensity of about 475 microeinsteins was used to make up the difference. Exposure temperatures were not precisely controlled, but averaged at approximately 29 ° C during the day and at approximately 21 ° C at night. The plants were sub-irrigated throughout the test to ensure adequate soil moisture levels.

The pots were assigned to various treatments in a totally randomized experimental design with 6 replications. A group of pots was left untreated as a reference against which the effects of treatment could be evaluated later.

The application of glyphosate compositions was done by spraying with a trace sprayer fitted with a 9501 E sharp flat fan spray tip calibrated to deliver a spray volume of 93 liters per hectare (I / ha) at a pressure of 165 kilopascals ( kPa). After treatment, the pots were returned to the greenhouse until ready for evaluation.

Treatments were done using dilute aqueous compositions. These could be prepared as spray compositions directly from their ingredients, or by dilution of preformulated concentrated compositions with water.

For the evaluation of herbicidal effectiveness, all plants in the test were examined by an individual expert technician, who recorded the percentage of control, a visual measurement of the effectiveness of each treatment by comparison with the untreated plants. The 0% control indicates no effect and the 100% control indicates that all plants are completely dead. The% control values reported represent the average of all repetitions of each treatment.

EXAMPLE 1 (not part of the invention)

The effect of glyphosate compositions on Commelina benghalensis (COMBE) was tested. Aqueous concentrated concentrations were prepared containing the listed amount of glyphosate salt in% by weight and excipient ingredients, as shown in Table 1a.

Table 1a.

The compositions from Table 1a and RT Master were applied to Commelina (COMBE). The results at 10 days after treatment (10DAT), 24 days after treatment (24DAT) and 41 days after treatment (41 DAT), averaged for all repetitions of each treatment, are shown in Table 1b.

Table 14b.

EXAMPLE 2 (not part of the invention)

The effect of glyphosate compositions was tested on Commelina benghalensis (COMBE) plants. Aqueous concentrate compositions were prepared containing the listed amount of glyphosate salt in% by weight and the excipient ingredients, as shown in Table 2a.

Table 2a.

The compositions from Table 2a, Ultra Blazer, Cobra and RT Master were applied to Commelina (COMBE). The results at 7 days after treatment (7DAT) and 24 days after treatment (24DAT), averaged for all repetitions of each treatment, are shown in Table 2b.

Table 2b.

This experiment shows that glyphosate and 2,4-D mixtures, such as 822B9T and RT Master, are more effective against Commelina than single ingredient formulations.

EXAMPLE 3

Aqueous compositions were prepared containing glyphosate potassium salt, IPA 2,4-D salt, and excipient ingredients, as shown in Table 19a. The formulations were prepared by mixing the aqueous solution of e.a. 40.5% w / w IPA 2,4-D at a% w / w concentration as indicated by [2,4-D] in Table 19a, surfactant (s), glycol, followed by adding aqueous solution of ea at 47.8 (47.4)% w / w of potassium glyphosate at a concentration in% w / w as indicated by [Gli] in Table 3a and then bringing the total volume to 100% with Water. The formulations were tested for cloud point and density.

Table 3a.

(continuation)

Additional aqueous compositions were prepared containing glyphosate potassium salt, 2,4-D acid, and excipient ingredients, as shown in Table 3b. The formulations were prepared by mixing the aqueous solution of 98% w / w ae of 2,4-D acid at a concentration in% w / w as indicated by [2,4-D] in Table 3b, surfactant (s), glycol, followed by the addition of aqueous solution of ae at 47.8 (47.4)% w / w glyphosate of potassium at a % w / w concentration as indicated by [Gli.] in Table 3b and then bringing the total volume to 100% with water. The formulations were tested for cloud point and density.

Table 3b.

EXAMPLE 4

The effect of glyphosate and combinations of 2,4-D and glyphosate on prepared Roundup® soybeans was tested at 1 day, 3 days and 7 days after treatment. Aqueous concentrated compositions were prepared containing glyphosate potassium salt, given in wt% e.a., and the excipient ingredients, as shown in the formulations in Table 3a above. The formulations were compared to RT Master® and Roundup Weathermax®. RT Master® and Roundup Weathermax® compositions and preparative compositions were applied to prepared Roundup® soybean plants. The results, averaged for all repetitions of each treatment, are shown in Table 4a.

Table 4a.

EXAMPLE 5

The effect of glyphosate and the combinations of 2,4-D and glyphosate on abutilon was tested. Aqueous concentrated compositions were prepared containing glyphosate salt, given in wt% ae, and the excipient ingredients, as shown in the formulations in Table 19a above. The formulations were compared to RT Master® and Roundup Weathermax®. Comparative compositions RT Master® and Roundup Weathermax® were applied to abutyl plants (Abutilon theophrasti, ABUTH). The results, averaged for all repetitions of each treatment, are shown in Table 5a.

Table 5a.

The order of efficacy for% ABUTH inhibition averaged for all application rates was 69.5A2D>646A8K>Weathermax>682A0M> RT Master> 656A1T.

EXAMPLE 6 (not part of the invention)

The effect of glyphosate and combinations of 2,4-D and glyphosate on abutilon was tested after 16 days of treatment. Aqueous concentrated compositions were prepared containing glyphosate potassium salt, reported in wt% ea, and the excipient ingredients, as shown in the formulations in Table 6a. The formulations were compared to RT Master® and Roundup Weathermax®. The compositions in Table 6a and the comparative compositions RT Master® and Roundup Weathermax® were applied to abutyl plants (Abutilon theophrasti, ABUTH). The results, averaged for all repetitions of each treatment, are shown in Table 6b.

Table 6a.

Table 6b.

EXAMPLE 7 (not part of the invention)

The effect of glyphosate and combinations of 2,4-D and glyphosate on abutilon was tested 15 days after treatment. Aqueous concentrated compositions were prepared containing glyphosate potassium salt, reported in wt% ea, and the excipient ingredients, as shown in the formulations in Table 22a. The formulations were compared to RT Master® and Roundup Weathermax®. Composition 935A8Z in Table 7a and comparative compositions RT Master® and Roundup Weathermax® were applied to abutyl plants (Abutilon theophrasti, ABUTH). The results, averaged for all repetitions of each treatment, are shown in Table 7a.

Table 7a.

The order of efficacy for% ABUTH inhibition averaged across all application rates was Weathermax> 935A8Z> RT Master.

EXAMPLE 8

The effect of glyphosate and combinations of 2,4-D and glyphosate on Roundup Ready® soybean plants was tested at 1 day and 3 days after treatment. Aqueous concentrated compositions were prepared containing glyphosate potassium salt, given in wt% ae, and the excipient ingredients, as shown in the formulations in Table 6a. The formulations were compared to RT Master® and Roundup Weathermax®. Compositions 681 C4J, 342B2H, 342C3A, 346A7C, 338A2W, 338B4F, 339A3Q and 341A7H in Table 3a and comparative compositions RT Master® and Roundup Weathermax® were applied to Roundup Ready® soybean plants (GLXMG) using an Al nozzle. The results, averaged for all repetitions of each treatment, are shown in Table 8a.

Table 8a.

The order of efficacy for the % control in Roundup Ready® soybeans averaged at all application rates using an Al nozzle was 339A3Q>338A2W>338B4F>341A7H>935A8Z> RT Master> Weathermax. EXAMPLE 9

The experiment in Example 8 was repeated using a TT nozzle to apply the formulations to the Roundup Ready® soybean plants. The results, averaged for all repetitions of each treatment, are shown in Table 9a.

Table 25a.

The order of efficacy for the% control in Roundup Ready® soybeans averaged over all application rates using a TT nozzle was 338AZW> 338B4F> 339A3Q> RT Master> 341 A7H> Weathermax.

Claims (16)

1. An aqueous herbicidal concentrate composition comprising: (a) glyphosate, predominantly in the form of the potassium salt thereof, in a concentration of at least 175 grams of acid equivalent per liter; (b) an auxin herbicidal component comprising one or more auxin herbicides selected from the group consisting of 2,4-D, dicamba, and agriculturally acceptable salts or esters thereof; (c) a first surfactant component in solution and comprising one or more surfactants selected from the group consisting of: (i) dialkoxylated quaternary ammonium salt having the Formula:

wherein R11 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R12 in each of the groups x (R12O) and y (R12O) is independently ethylene or propylene, R13 is hydrogen or methyl, R14 is a straight or branched alkyl group having 1 to about 6 carbon atoms, the sum of x and y is an average number of about 2 to about 15, and X- is an agriculturally acceptable anion; (ii) monoalkoxylated quaternary ammonium salts having the Formula:

wherein R21 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R24 and R25 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms, R22 in each of the groups x2 (R22O) is independently ethylene or propylene, R23 is hydrogen or methyl, x is an average number from about 5 to about 25, and X- is an agriculturally acceptable anion; Y (iii) quaternary ammonium salts having the Formula:

wherein R31 is a linear or branched alkyl group having from about 8 to about 16 carbon atoms and R32, R33 and R34 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms and X- is an agriculturally acceptable anion. 2. The composition of claim 1, wherein the first surfactant comprises (i) monoalkoxylated quaternary ammonium salts having the Formula: R25 X ' R21 ---- N + ----- (R220) ^x 2R23 (3) R24 wherein R21 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R24 and R25 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms, R22 in each of the groups x2 (R22O) is independently ethylene or propylene, R23 is hydrogen or methyl, x is an average number from about 5 to about 25, and X- is an agriculturally acceptable anion; or (ii) quaternary ammonium salts having the Formula:

wherein R31 is a linear or branched alkyl group having from about 8 to about 16 carbon atoms and R32, R33 and R34 are independently a linear or branched alkyl group having from 1 to about 6 carbon atoms and X- is an agriculturally acceptable anion. The composition of claim 1, wherein the glyphosate (acid equivalent base) and the auxin herbicidal component (acid equivalent base) are present in a weight ratio of at least about 5: 1. The composition of claim 3, wherein the glyphosate (acid equivalent base) and the auxin herbicidal component (acid equivalent base) are present in a weight ratio of at least about 30: 1. The composition of claim 4, wherein the glyphosate (acid equivalent base) and the auxin herbicidal component (acid equivalent base) are present in a weight ratio of at least about 60: 1. 6. The composition of claim 1, wherein about 90 percent by weight of the glyphosate is present as the potassium salt thereof. The composition of claim 1, wherein the glyphosate is present in an amount of at least about 325 grams of acid equivalent per liter. The composition of claim 1, wherein the glyphosate is present in an amount of at least about 425 grams of acid equivalent per liter. 9. The composition of claim 1, wherein the glyphosate is present in an amount of at least about 525 grams of acid equivalent per liter. The composition of claim 1, wherein the total surfactant present in the composition is in an amount of at least about 5% by weight based on the total weight of the composition. The composition of claim 1, wherein the glyphosate (acid equivalent base) and the first surfactant component are present in a weight ratio of from about 1.9: 1 to about 6: 1. 12. The composition of claim 1, wherein the composition has a cloud point of at least about 50 ° C. The composition of claim 1, wherein the composition has a crystallization point of no greater than about 0 ° C. The composition of claim 1, wherein the herbicide content consists of glyphosate or a herbicidal derivative thereof and the auxin herbicidal component. 15. The composition of claim 1, wherein the composition further comprises a solvent organic, said composition containing no more than 10 percent by weight of said organic solvent based on the total weight of the composition. 16. A method of killing or controlling unwanted weeds or vegetation comprising: diluting the composition of claim 1 in an amount of water to form an application mixture; and applying a herbicidally effective amount of the application mixture to weed foliage or unwanted vegetation.